Intermolecular interactions found in the Cambridge Structural Database (CSD) are analysed as the outcomes of competitions between the different functional groups that are present in each structure: the most energetically favourable interactions are expected to win more often than weaker interactions. Tracking winners and losers through each crystal structure in the CSD provides data that can be analysed using paired comparison algorithms to rank functional group H-bonding properties based on how frequently they outcompete other functional groups in the crystal. This treatment is superior to simple statistical analyses of whether functional groups H-bond or not, because the distribution of H-bond donors and acceptors in the structures of the molecules found in the CSD is non-random. Most organic molecules contain more acceptors than donors, so that all H-bond donors are almost always H-bonded in all crystal structures, and most acceptors are not. The rankings of H-bond acceptors obtained by applying the TrueSkill paired comparison algorithm to the CSD agree well with the corresponding experimentally determined solution phase H-bond acceptor parameters β, but there is insufficient data to corroborate H-bond donor rankings calculated in the same way. The method is used to make predictions of the H-bond acceptor properties of functional groups for which solution phase measurements are not available.Engineering and Physical Sciences Research
Council, Cambridge Crystallographic Data Centr
